Process and preparations for producing prints with azo dyestuffs being insoluble in water



United tates Patent '0 PROCESS AND PREPARATIGNS FQR PRODUCING PRINTS WIIH AZt) DYETUFF S BEING INSUL- UBILEIN WATER Josef 'Riedmair, Frankfurt am Main-Fechenheim, Herbert Rein, Frankfurt amMain, and M x Kcrth, Rad oden (Taunus), Germany; Margarete Rein, ne Thiebac'h, executrix of said Herbert Rein, deceased, assignors to CassellalFarbwer-ke Mainkur Alstiengeseiischaft, rankfurt am'Main-Fechenheim, Germany .No Drawing. Application October 7, 1952, Serial No. 313,583

'4 Claims. (Cl. 8- -71) Thisinvention relates to a process for producing prints with azo dyestuffs being insoluble in water and to preparations u-sed inthis process.

It is known as a technically important process for producing prints on textile materials that mixtures of coupling components with such diazoamino compounds which contain water-solubilizing groups in the residue not taking part in the dyestuff formation are dissolved in alkali lye, brought into a form suitable for textile printing by the addition of thickening agents, etc., printed onto the fiber and exposed on the fiber to the action of acid vapors at elevated temperatures. Under these conditions the diazoamino compounds are cleaved and coupling takes place between the diazo compounds thus formed and the coupling components.

This so-called acid steam developing method, however, has a number of deficiencies; for example corrosion of equipment, lack of ability to be combined with vat dyestuffs, etc. Therefore, various attempts have already been made to replace the coupling conditions by a simple treatment with neutral vapor.

Thus, it has been suggested to add substances to the printing pastes which will liberate an acid during the heat treatment, e. g. salts of halogenated fatty acids (German Patent 640,935 and British Patent 454,869). Printing pastes thus produced have in some cases a good storage stability, as e. g. in case of the addition of anonochloroacetic salts; they require, however, after printing onto the textile fiber a prolonged steaming time not acceptable in practice. When on the other hand salts of halogenated fatty acids being capable of a more rapid cleavage are used, c. g. salts of bromoacetic acids or the salts of halogenated succinic acids, it is true that dyestuif formation occurs more rapidly, but here again an unsuflicient storage stability is encountered because these substances are subject to hydrolysis already after a short time at room temperatures.

Now the surprising discovery was made that by the addition of salts of the a,a'-dichloroadipic acid, which has not yet become known from literature, or of. its derivatives which are capable of transformation into salts (such as e. g. esters, amides), printing pastes are obtained which have both an outstanding stability at room temperature and the ability of furnishing intense and pure shades after having been printed onto the textile fiber and having undergone a short treatment with neutral vapor as is common in practice.

Therefore, it is one of the objects of the present in vention to provide an alkali salt of a,a-dichloroadipic acid as an ingredient of printing pastes.

Another object of this invention are preparations consisting of (a) diazoamino compounds in which the residue not taking part in the dyestuit formation contains watersolubilizing groups, (b) azo coupling components, a compound of the group consisting of alkali metal salts of u,et-dichloroadipic acid and agents delivering such salts by the action of caustic alkali.

2,786,731 Patented Mar.- 26, 1957 A further object of this invention are printing pastes prepared .by dissolving mixtures of the aforesaid diazoamino compound and 2120 coupling components in alkali lye and adding thereto a,a'-dichloroadipic acid or a derivative thereof delivering in the presence of caustic alkali an alkali salt .of this acid and furthermore adding the usual ingredients as thickening agents etc.

The a,a'-dichloroadipic acid, having a melting point of 176l78 C., may be produced e. g. by the action of the necessary quantity of chlorine on adipic di' chloride at 95100 C. and saponifying the oc,a'di(:hl01'0- adipic dichloride produced with strong hydrochloric acid. t

The a,ot-dichloroadipic dimethylester may be obtained e. g. by the action of methanol on the chlorination product of adipic dichloride. It is a colorless oil which boils under a pressure of 1 millimeter mercury pressure at lid-116 C.

The following examples are given for the purpose of illustrating the invention, the parts being parts by weight.

Example .1

parts of an equimolecular mixture containing l-aceto-acetyl-amino-4-chloroa2.S-dimethoxybenzene and the diazoamino compound of diazotized S-chloro-Z- amino-l-methylbenzene and methylamino-ethane-sulfonic sodium, are made into a paste, or dissolved, with 50 grams of urea, 30 grams of spirit, 30 grams of caustic soda lye 38 B. and 140 grams of hot water. To the solution there are added 500 grams of neutral wheat starch tragacanth thickener in which 80 grams of ,0!- dichloroadipic acid have been neutralized previously with grams of caustic soda lye 38 B.

Prints produced with this printing paste develop in steaming with neutral vapor within about 5 minutes to a clear intense yellow shade, while a printing paste containing instead of the a,a-dichloroadipic acid an equivalent amount of monochloroacetic acid does not lead to a useful result, neither after 20 minutes of steaming.

The printing paste prepared according to this example has a very good storage stability at room temperature.

Example 2 Example 3 80 grams of an equimolecular mixture of 1-(2'3- hydroxynaphthoyl-amino)-2-methoxybenzene and the diazoamino compound from diazotized 4-chloro-2-amino-lmethoxybenzene and the methylaminoacetic sodium give, when using the process outlined in the previous examples, stable printing pastes which after printing onto the fiber produce in steaming after only a short time a clear, intense red shade, whereas when using instead of mod-dichloroadipic acid the equivalent amount of monochloroacetic acid no notable dyestutf formation occurs.

Example 4 50 grams of an equimolecular mixture of 2,3-hydroxynaphthoylaminobenzene and the diazo amino compound from diazotized 3-amino-6-benzoylamino-4-methoxy-1- methylbenzene and methylaminoacetic sodium are dissolved in a similarway as indicated in the above examples with 50 grams of urea, 30 grams of spirit, 25 grams of caustic soda lye 38 B. and about 125 grams of warm water. 7 7

To the solution there are added 500 grams of neutral wheat starch tragacanth thickener, which has previously been stirred with 90 grams of a,a'-dichloroadipic dimethylester and 90 grams of caustic soda lye 38 B.

The printing paste thus obtained, which is stable at ordinary temperatures, produces after printing onto the fiber with steaming for 5 minutes a substantially more intense blue shade than is obtained when replacing the a,a'-dich1oroadipic dimethylester by the equivalent amount of monochloroacetic acid.

Example 5 80 grams of an equimolecular mixture of 2,3-hydr0xycarbazole-carboxylic-4-chloroanilide and the diazoamino compound from diazotized 4-chloro-2-amino-l-rnethoxybenzene and methylaminoacetic sodium yield, when following the same method of operating as in the previous examples, a significantly more intense brown shade than is obtained by the process using monochloroacetic acid.

We claim:

1. Dye printing pastes in which the dyeing ingredients consist essentially of (a) a diazoamino compound of a diazo material with an amine that contains a water solubilizing group, (b) an azo coupling component, and (c) an alkali metal salt of the a,o-dichloroadipic acid that melts at 176178 degrees C.

2. A diazoamino dyeing composition in which the dyeing ingredients consist essentially of a diazoamino dye compound, an azo coupling component and as an agent that increases the acidity upon steaming, a compound selected from the class of dialkyl esters and dialkali metal salts of the alpha,alpha' dichloroadipic acid that melts at 176-178 degrees C.

3. The method of azoic printing which includes the steps of printing on a fabric a composition comprising a diazoamino compound, a coupling component and an acid developing agent selected from the class of dialkyl esters and dialkali metal salts of the alpha,alpha dichloroadipic acid that melts at 176-178 degrees C., and developing the dye by neutral steaming to cause the aciddeveloping agent to develop acid.

4. The method of. printing textiles which includes the steps of applying to the textiles an acid-developing dye paste containing a diazoamino compound, an azo coupling component, and an alkali metal salt of the alpha, alpha dichloroadipic acid that melts at 176 to 178 C., and subjecting the textile carrying the applied paste to a neutral steaming operating to cause the alkali metal salt to liberate acid and develop the dye.

References Cited in the file of this patent UNITED STATES PATENTS 2,088,506 Chambers July 27, 1937 FOREIGN PATENTS 242,837 Switzerland Nov. 1, 1946 

4. THE METHOD OF PRINTING TEXTILES WHICH INCLUDES THE STEPS OF APPLYING TO THE TEXTILES AN ACID-DEVELOPING DYE PASTE CONTAINING A DIAZOAMINO COMPOUND, AN AZO COUPLING, COMPONENT, AND AN ALKALI METAL SALT OF THE ALPHA, ALPHA'' DICHLOROADIPIC ACID THAT MELTS AT 176 TO 178*C., AND SUBJECTING THE TEXTILE CARRYING THE APPLIED PASTE TO A NEUTRAL STEAMING OPERATING TO CAUSE THE ALKALI METAL SALT TO LIBERATE ACID AND DEVELOP THE DYE. 